Sulfuric acid/sulfonated phenolics

SULFURIC ACID/SULFONATED PHENOLICS (Debacterol liquid 30% sulfuric acid and 22% sulfonated phenolics)... 

Sulfuric acid/sulfonated phenolics is a mouth-and-throat product. Sulfuric acid is a tissue denaturant and sterilizing agent. Sulfonated phenolics are antiseptic agents with... 

In the benzene sulfonation process, benzene reacts with concentrated sulfuric acid to form benzenesulfonic acid at about 150°C. The benzenesulfonic acid is neutralized with sodium sulfate to produce sodium benzenesulfonate, which is then fused with caustic soda to yield sodium phenate, which, after acidification with sulfur dioxide and a small amount of sulfuric acid, releases phenol from the sodium salt. 

Another still more recent process which starts with cumene (isopropyl benzene) has attained considerable prominence. It does not involve hydrolysis, but consists of the oxidation of cumene to the hydroperoxide and the subsequent decomposition of the latter by sulfuric acid to phenol and acetone. Like the sulfonation process, it depends for its commercial success upon the sale of its by-products, chiefly acetone. 

Sulfonation Heating a phenol with concentrated sulfuric acid causes sulfonation of the ring... 

Ca.ta.lysis by Protons. The discovery of hydrogen peroxide hydroxylation of phenol in the presence of strong acids such as perchloric, trifluoromethane-sulfonic, or sulfuric acids allows suppression of all previous drawbacks of the process (18,19). This mode of hydroxylation gives high yields (85% based on H2O2 at phenol conversion of 5—6%). It can be mn without solvents and does not generate resorcinol. Its main advantage rehes on... 

The reaction is completed after 6—8 h at 95°C volatiles, water, and some free phenol are removed by vacuum stripping up to 140—170°C. For resins requiring phenol in only trace amounts, such as epoxy hardeners, steam distillation or steam stripping may be used. Both water and free phenol affect the cure and final resin properties, which are monitored in routine quaHty control testing by gc. OxaHc acid (1—2 parts per 100 parts phenol) does not require neutralization because it decomposes to CO, CO2, and water furthermore, it produces milder reactions and low color. Sulfuric and sulfonic acids are strong catalysts and require neutralization with lime 0.1 parts of sulfuric acid per 100 parts of phenol are used. A continuous process for novolak resin production has been described (31,32). An alternative process for making novolaks without acid catalysis has also been reported (33), which uses a... 

Dyes, Dye Intermediates, and Naphthalene. Several thousand different synthetic dyes are known, having a total worldwide consumption of 298 million kg/yr (see Dyes AND dye intermediates). Many dyes contain some form of sulfonate as —SO H, —SO Na, or —SO2NH2. Acid dyes, solvent dyes, basic dyes, disperse dyes, fiber-reactive dyes, and vat dyes can have one or more sulfonic acid groups incorporated into their molecular stmcture. The raw materials used for the manufacture of dyes are mainly aromatic hydrocarbons (67—74) and include ben2ene, toluene, naphthalene, anthracene, pyrene, phenol (qv), pyridine, and carba2ole. Anthraquinone sulfonic acid is an important dye intermediate and is prepared by sulfonation of anthraquinone using sulfur trioxide and sulfuric acid. 

Toluenesulfonic Acid. Toluene reacts readily with fuming sulfuric acid to yield toluene—sulfonic acid. By proper control of conditions, /)i7n7-toluenesulfonic acid is obtained. The primary use is for conversion, by fusion with NaOH, to i ra-cresol. The resulting high purity i7n -cresol is then alkylated with isobutylene to produce 2 (i-dii-tert-huty -para-cmso (BHT), which is used as an antioxidant in foods, gasoline, and mbber. Mixed cresols can be obtained by alkylation of phenol and by isolation from certain petroleum and coal-tar process streams. 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

N.C6H3(0H).S03Na, mw 241.16, N 5.8%, orange-red crysts. Can be prepd by treating the product obtained on sulfonation of phenol with Na nitrate and an excess of sulfuric acid. This salt, which is a mixt of Na o- and p-nitrophenol-sulfonates, was patented in 1911 by A. Voight for use in expl mixts such as Na nitrophenol-sulfonate 22.5 to 25, K or Na nitrate 45 to 65,... 

Phenol was originally recovered during the coking of coal, essentially being a by-product. Eventually, commercial routes were developed based on benzene (from coal or petroleum) for example, sulfonation of benzene to ben-zenesulfonic acid followed by reaction with water to phenol plus regenerated sulfuric acid. Phenol is used to make plastics (phenol-formaldehyde and epoxy resins) and textile fibers (nylon). Phenol is also used in solution as a general disinfectant for cleaning toilets, stables, floors, drains, etc. and is used both internally and externally as a disinfectant for animals. 

Tyrer A process for making phenol by first sulfonating benzene. Benzene vapor was passed through hot sulfuric acid the excess of benzene served to remove the water formed in the reaction. The benzene sulfonic acid was then hydrolyzed by fusion with sodium hydroxide. Invented by D. Tyrer in 1916. See also Dennis-Bull. 

This procedure is based on the method of Smith, Opie, Waw-zonek, and Prichard3 for the preparation of 2,3,6-trimethyl-phenol. 3-Hydroxypyrene has been prepared by fusion of pyrene-3-sulfonic acid with sodium hydroxide 4 and by desul-fonation of 3-hydroxypyrene-5,8,10-trisulfonic acid with hot, dilute sulfuric acid.5... 

These carbonaceous catalysts can be obtained by the sulfonation of incompletely carbonized organic compounds [42]. Note that starch and cellulose can be used as carbon precursor [43, 44]. After the incomplete pyrolysis of the carbon precursor, the SO3H groups have been introduced by sulfonation with sulfuric acid (Scheme 3). After this treatment, the presence of phenolic hydroxyl, carboxylic acid, and sulfonic groups at the surface of these amorphous carbonaceous materials has been demonstrated. 

Phenol was prepared before World War I through the distillation of coal tar. The first synthetic process involved the sulfonation of benzene followed by desulfonation with a base. In this process, benzene sulfonic acid is prepared from the reaction of benzene and sulfuric acid ... 

Diary,I sulfones. Sulfuric acid and trifluoroacetic anhydride (1 2 equivalents) form bis(trifluoroacetyl) sulfate (1). which converts arenes and phenol ethers into diaryl sulfones in 70-99% yield. 

Sulfuric acid acts as an inhibitor or moderator of the nitration. The sulfonation of phenol at low and high temperatures produces the ortho-and para-sulfonic acids, respectively. All these substances yield picric acid as the final product of the nitration. 

Sulfonation of Benzene and Alkylbenzenes. Since the main utilization of ben-zenesulfonic acid was its transformation to phenol, the importance of the sulfonation of benzene has diminished. The process, however, is still occasionally utilized since it is a simple and economical procedure even on a small scale. Excess sulfuric acid or oleum is used at 110-150°C to produce benzenesulfonic acid.97,102 Sulfonation of toluene under similar conditions yields a mixture of isomeric toluenesul-fonic acids rich in the para isomer. This mixture is transformed directly to cresols by alkali fusion. 

Most of the phenol used in the United States is made by the oxidation of cumene, yielding acetone as a byproduct. The first stqn in the reaction yields cumene hydroperoxide, which decomposes with dilute sulfuric acid to the primary products, plus acetophenone and phenyl dimethyl carbinol. Other processes include sulfonation, chlorination of benzene, and oxidation of benzene. The compound is purified by rectification. 

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